Reduction of the sulfur content of certain high boiling petroleum fractions ...

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Title:
Reduction of the sulfur content of certain high boiling petroleum fractions ...
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55 leaves : ; 28 cm.
Language:
English
Creator:
Gary, James Hubert, 1921-
Publisher:
University of Florida
Place of Publication:
Gainesville, Fla
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Subjects

Subjects / Keywords:
Petroleum -- Refining   ( lcsh )
Organosulfur compounds   ( lcsh )
Genre:
bibliography   ( marcgt )
theses   ( marcgt )
non-fiction   ( marcgt )

Notes

Bibliography:
Bibliography: leaves 53-54.
Statement of Responsibility:
By James H. Gary.
General Note:
Manuscript copy. Typed on one side of leaf only.
General Note:
Dissertation (Ph. D.) - University of Florida, 1951.
General Note:
Biography.

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University of Florida
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All applicable rights reserved by the source institution and holding location.
Resource Identifier:
aleph - 000541686
notis - ACW5231
oclc - 13077622
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AA00003988:00001

Full Text











REDUCTION OF THE SULFUR CONTENT

OF CERTAIN HIGH BOILING

PETROLEUM FRACTIONS









By
JAMES H. GARY










A DISSERTATION PRESENTED TO THE GRADUATE COUNCIL OF
THE UNIVERSITY OF FLORIDA
IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE
DEGREE OF DOCTOR OF PHILOSOPHY










UNIVERSITY OF FLORIDA
June, 1951












kCri L.;L .-G .-: CIHT


The autihor wishes to express his sincere appreciation

to Dr. Hi. iE. Schweyer for his seiulous and considerate

guidance as director of the research. The author is also

indebted to ::r. T. %. Leeper and .'.r, A. 0. ..ikman for their

many helpful criticisms; to Dr. R. A. ."orr-en for tho use

of tho facilities of the Engineering and Industrial

-:xperi.aent .atction; ani to tl-,e r.e.bers of his Supervisory

Co.iiittee, Dr. *ack Tyner, Dr. A. .'-lp, s, Dr. aul Tarrant

-n irrofossor P. L. Ircscott for t'eir reco-i-.endations and

assistacnce. The aut: or wishes to exprars appreciation to

CitiLs Service .reflnlng Corporation, .sso it rdard oil

Co.:.uny, Gulf i'll Cor-:.oration, ..a;.nolia petroleum Go',"fpany,

an-i tre Standard o.il Comp':ny (Indiana) for f'urnisiinug tne

sa-.ples of hiigh-sulfur cas oils use. in tPe inv:stiution.


(1)










TABLE OF C0cNTENTS


rage

ACKNu .LLEDG)c-.iENT (1)

LIST F FIGURSS (ili)

LIST OF TABLES (iv)

I INTRODUCTION 1

II STAli;..ENT OP THE t8 ,ILM 8

III LITrATRA'fUhRE R:VI-W

h-. Chromatopraphic adsorption 9

B. Desulfurization 12

C. Sulfur Analysis 16

IV DESCII'lTIU!O OPr AUrrA'.'.T7US

A. Deaulfurization Unit 17

B. Adsorption Apparatus 24

V PROC EDURE

A. Desulfurization Apparatus 26

B. Adsorption Apparatus 28

C. Sulfur Analysis 31

D. EKxperimental Data 33

VI RESULTS 35

VII CUIoCLUSIONS 52

VIII BIBL IOGRH.iY 53

IX API- EiDDI 55


(ii)











LIST ut .I;U 'oS


F'i -ure Title rage
.o.

1 'nite.3 t-.tes Crude Oil i'roductlon 2

2 Nieactor ri.otorraph 18

3 ijosulfu.rizer Flow lia:ran 19

4 L..actor Scne.iatic *. 21

b .;-x.ctor heater iring Diagram 22

6 .dsorption Column 25

7 Typical refractive Inde'x Curve 0 50

8 .isorption : r;ctions 32

'J iJsuliuriz :tin of J-as .is 41

10 e.-:ulfurization of i-.-s i..iil I'rctions 41

11 ,ulfr distributionn 'a e 3-121 43

12 Julfur Distribution, *;*.iple 5-126 44

13 sulfur distribution, Jam]ple r-162 44

14 ..L llur AijLtribution, aiple '-129 4b

15 1;ulfur Distribution, n .in le Gl-153 45

1G .uil'.r lAstribution, Sa i!ple '-128 46

17 .ulfur istrrihution, ,a&mpleO '3-137 46

18 .:ulfur Jistribution, sample 3-100-F 47

19 .*.ifur distribution, .s ::.lo :-134 48

0O .i [fur :iLatrLbution, ple --1l5 ,* 48

1 Co ...-oL.iti 'n C'.une .it-: VI c'slt: oO

22 c.> oastiorn : '.n;-e witt, V'sc- slty 1


(111)


















LIST OF TABLES


Table Title Page
0o.

1 Sulfur Compounds in Oil 5

2 Desulfurization Feed Stocks 37

3 Adsorption Feed Stocks 38

4 sulfur Distribution 39

5 Desulfurization Conditions 56

6 Adsorption Data 60


(iv)










I. iPNTRiUDTTC'TIUL


F'or many yec~rs the petroleum industry has been

face with- tie proble.!s i-l.oseai 1pon it by the presence

or various tr;;es of sulfur co r-nounis in crude oils

processed in the refineries. The need for effective

met: ods for re..:ovinr, sulfur from oils constantly is

.rowin, -.ronter for several reasons. As tlhe reserves of

low-sulfur crude oils decrease, the refiner is forced to

use more and .iore of the hir-h-sulfur crudes in order to

-:rintain or increase the ar.ount of his products. .ven for

those refi-era lwo have been proces:'inr sour crudes for a

number of years, the increase in sulfur content of the

refinery ciarire st-ck:s Ias aa anified and multiplied the

number :nf pirobleis normally encountered. In -'i ure 1 are

.lote. curves, p;ublisred ori '.-nullly by ::aith and -ilade (2d),

;.d aubs o. ue-tly r".vised by ti-Lem (2-1), 3rs' .:n;. ti.e production

ci crule oils of various r.ulfur contents in the United -tates

du:'ir- te puziod fromr. 1916 to 1947, *s of the end ol 1947,

a,,rxi xatly t l.j2 Tnilllolr barrels o' L.e 1,'"o million barrels

of crulo oil ,ro.tuced annually In the I: Lted states s contained

u.ver t,. .-.e cent sulfur -.n: over 70 t7C, lli n barrels

cont.air.ci over 0.b5 sulfur, 'i'e increased production of !.I.;h-

siLt'Lir cru.les in ti;. Id 1i .:.sst an.ul south .,merica has ad ed

to i.il .r.,LI r. cn': i eraIly since it a npours that most of

ur..pe's 'uiur'.-- re ,rii Ol* ts :ust :ieccss.arily be supplied








Figure 1

Crude Oil Production for the United States




1800.


1600
Legend
S>2.0 % Sulfur
91400 -
1400 0.51-.0 $ Sulfur --
FM0.26-0.50 % Sulfur
o 1200 -
01 01- 0 -0,25 % Sulfur


l ooo
800 *--- ----------* /*--- ------ -


o .. .... _.
61000--------- ---I---------- -p ----
I II




400
800
| 600 --- ---- ^- -^ -






200 R l



1915 1920 1925 1930 1935 1940 1945 1950
YEAR









from these sources. The large reserves of shale-oil

located in thLe western parts of che United States and

Canada are also hlsh in sulfur content. Before these oils

can assume the importance w..ich is forecast by the large

reserves available, a satisfactory solution to the sulfur

problem must be obtained,

Several of the most im.:ortant problems due to the

presence of sulfur con-ounds in petroleum are (12):

1. Corrosion of refining, storage ani
transportation eouipmnont.

2. lliminacion of odoriferous sulfur
co'-.pounds from products.

6. ;curession of octane ratings.

4. ioductlon of load susceptibility,

b. Increased *--ir rates of engines.

6. Catalyst poisr.ning during: catalytic
procesjln.. of the crude oil cuts.

7, Adrverse effects on product stability and
burntlr ciluracteristtcs,

Ailt:oul.- tna jresonce of sulfur causes man crude oils

to be clas.ilfled as "manr::lril" because of the above un-

ieslr.ble characterintics, t'.e petrolou:n industry is l'ining

it necessary to use such u .troleums to satisfy present needs.

.:1us, tLi nee for fund -rital reset-rch on the removal of

sulfur fr. : etroleum !--roducts In bocoing '-reater as t:o

in!unt.ry Is forco1 to call upon all available resources to

eelt te dr rand for retrolour! products.

greatt number of studies have been rnimde on the types

of sullL r co ound-s found in 'etroleum and shale oils but









it is apparent from a study of the literature that a

large amount of fundamental information is still lacking.

There is considerable disagreement as to the types of

sulfur co.Ti.ounris tjnat may occur in crude oils :.rnd straight-

run distillates. 'j'here is also some (;uestlon as to whether

the types t:;at arr known to be present occur as such in

the original petroleum or are formed .iurinpe- distillation.

A summary of the available ikno':leige on the occurrence

of various types of ~ ulfur co':iyounds in oils is .shov.n in

Table 1 (1, 12). From t.h -.e datP several 'ener: liz.-tions

can be m-lade. The pros nce of thiols (rnercs1tans) and

disulfides is well established, :-ith saturated co.ipounds

predominatin,g in straight run iistillates ani aromatic

derivatives prodominattin, in cracked 11istillates. N;o

aro!natic sulfides have been isolated; prob,'bly due to the

fact that the first Lmemnber of this series has a relatively

hi.:h boiling point. ''he ..r
run distillates is questionable, but t 'elr prcs-nco in

cracked distillates has been well established. No co;i.,pounds

containing more than one sulfur atom to tie riolecule, other

tnan disulfides, have as yet be.n isolated from petroleum

sources (''),

The methods for removal of sulfur from petroleum oils

may be separated into two types; those which remove the

entire molecule containl;-:- the sulfur anJ trnose i hlch rc-.ove

only the sulfur. In general, the first type of process is












Table 1

Sulfur Compounds in Oil


*: :Stra!-iht:
SType Formula :Crude: Hun :Cracked


Sulfur S + : + : +
hydrogen L.ulfide Hg2S : + : + : +
P i t
,; ercauptans 3: :
Aili.lhattic+ Mi. KH : + 3 + 3 4
pht!,enic : i1 : : :
Aromniatic : iSi : ? : +

,-ulf ides : 3 :
.-.li' i.Ltic R..-i : ? : + : +
i.... it- ,::ic : <-;.-'- : 7 + : T
..ro. ati c : ,-:.j- : : i

liuifides :
,l.i.nhatic : -.-..-.i : ? : + : -
.-ro.at ic : -:J- : ? : : +


1 0 v
tn1 .olo.a : 3 I

* olys:.,fid, -a -: : + +
o.y..ui.._1's : 3 _._ +-_^ +______ ;


+ ;.iilf)Iu Co n7oun) res -nt
- nif\iir .:oi;ioun i .bs..-nt
T7 I'n'~novn or u-1. tionable









used for .Litht distillates and the latter for de-

sulfurization of gas oils. This is due to the fact t;:at

it is important from the refiner's st_ -r-ioint that the

sulfur be removed in such a ,i.nner tiat the volume of

nte oil bnin)- d sulfurizod is not rnar.:eai.L. roeucetd. in

tie case of the liiht distillates where trio average number

of carbon atoms per molecule is a,' .roximately six, the

sulfur atom comprises a larog part of the molecular wuijit.

Thus tiie Ai;ole molecule can be removed without appreciably

affectin- the volume. In t1nr ctis,. of t-he gas oils, the

number of carbon atoms per molecule is in the range of

thirty to sixty a a an oil havin- five wei .t per cent

sulfur content ;ay contain twenty-five to fifty per cent

sulfur co.,iJounds (12), heM,-oval of the sulfur colnpounds as

such would be economically unattractive in this case.

'iiie entire sulfur cor...ound may be r,-!oved by caustic

wa:fi-in,;, acid treating (1), or extraction with hydrogen

fluoride (14). At trie present time the only method

known for complete dusulfurizatlon of petroleum oils by

res.-oving only tne sulfur is some form of catalytic hydro-

urenation in rhich the sulfur is r-mnoved as hydrogen sulfide

and the. remainder of the sulfur beprinrf molecule is converted

to a hydrocarbon. '..ssentially all of these processes are

similar, with the operaLinr- conditions varying according to

the typc of catalyst used. Data have been pubilisied on such

catalysts as fuller's earth (1), nickel-tlunsten sulfites (4),




7





a!ici-:el-molybdenu- sulfides (23), bauxite (J), cobalt

molybdate (2), ..n.i 7Pnc-,iolybdenurr, bauxite ('J), uf

these Cutlytic .etnods, the cobalt i:olybdate process

is t:.t one r,.ost corrm ,letel. ex lined in the literature.











II. STTEI.T.UNT OF TPT -: V RuBL

There were two purposes of this investigation. The

first was to determine how the sulfur contoe:t of the gas

oil fractions of a variety of crude oils is distributed

among the paraffin, naphthene, and aromatic fractions.

The second pur!rose was to determine the mr.nner in which

the desulfurization by hydrogenation affects the

distribution of sulfur,

The investigation was divided into two phases; one of

analysis and the other of desulfurization.

The separation of the gas oils into their paraffin,

naphthene, and aromatic components was accoliiplished by use

of the chromato:.raphic adsorption method developed by tihe

United ,tates bureauu of standards. ''he sulfur content was

determined by use of the high temperature co:nbustion-

titration prou ..ure adopted by .america.n society for Testing

materials.

'The ras oils were desulfurized by the low pressure

hydrorfonation method developed by the Union Oil Company which

uses a cobalt-molybdate catalyst. Operating conditions vere

selected within the range of their development data in order

that the effect of the change of operating variables would

be known. All samples were desulfurized at the same

operating conditions.










III. LIT ':-ATUR-. RTVI-%.

A. Chronatographic Adsorption

The ;:ethod of adsorption ussi to separate petroleum

fractions Into their various mrolecular types is essentially

t.iat devise by the r.uasian botanist M. Tswett and is

cocinonly known as the iswett methlod or the cliromnatographic

mnot'od. rrovious applications of ti:is r:.ethod to the

separation of nron tic hydrocarbons involved principally

hydrocarbons o! hi[.h tlolecular wl-.,iht an.-l of biological

i.,-ortance, .ork by ;.'air and associates showed that

fractionation by aisorptlon could be used to obtain

separation of petroleum fractions in the -asoline (15),

kerosine (16, 17), and &.as oil (19) ranges into t:.eir

;.,clecl lar types of compoundls.

The adsor ticn method consists, in -cnoral, of

a:lsorbir. the -"aterial to b- aSlparated on a suitable

adsorbLnt, usually silica gel, then a suitable desorbing

liquid is introduced. 'ho dosorbing liquid forces the

hydrocarbon portion lown the column of adsorbent causing

trio hydrocarbo portion to be fractionated according to

uhe a sorb:,bilit:,, of the various co:.pononts, 'These

co:.~ionents issue fro.. the bottom of the column in the

following order: ari ffLn, n-i;ht..ne, rnd nror.iatic.

'';e successful a.iplicttion of this toc!nique requires

a desorbr.nt that till qu:i:titAtlvcly remove the hydro-

cu.rLbo- fro the adsorbent, Goodinrt. rnd opkins (7)










have pointe- out that the characteristics desirable in a

desorbant are:

1. A stren.thi of adsorption greater than any
co;nponent of the sample

2. A viscosity higher than that of any component
of the sample

3. Complete iniiscibility v.'ith the aromatic portion
of the sample

4. A refractive index sufficiently different from
the aromatic portion that the final break on
the adsorptogram may be determined satisfactorily,

>hen separating petroleum fractions in the gas oil range,

it is virtually il- ogsible to fi-d a 'lesorbant fulfilling

completely all of the requir.-ments. Desorbsnts used for

tnis purpose are ethanol (13), cyclohexanl (i.),

1-octanol (5), aind n-henanol (19).

reductionn of the time required for analysis by raising

the temperature at which it is conducted is desirable and

it may be necessary to ise an elevated tem;.erature in the

case of a gas oil having a high pour point, Analyses

made by the same procedure on the same samples at room

temperature anfi at 7000. showe- no significant difference (b).

However, it was found necessary to maintain relatively close

control of the temperature of operation in order to prevent

remixing of the components.

Liquids which serve as desorbants or developors may be

classified into two -roups de;-ending upon their strength of

adsorption in relation to the material bein. sep;Lrated (3),










The desorbants which displace absorbed material from the

column by virtue of their -reater strength of adsorption

are cLAled dis-lacents. In such an operation, the desorbed

material is caused to move down the colutin asead of and

at tie samei rate as the displaoent. The less strongly

Eaisorbed dovrlclers are tcr-ned eluents. 'ihey will displace

c'.e i:araffin -.nd na;-hthene hydrocarbrns but not the aromatic

:- Iroaoirbons. 'ne paraffiris, napihthenes, an-i eluont

cr:r obtained as a Aixture fror.i which the eluent is separated

by distillation. 'ihe aronatic portlirU is tr n removed from

tLn ai~orbent by us of a disi.lacent.

ihe size anUi s;:ia-e of the a sor;jtion column is s~-cifled

by tLe :.uru.'u oi'f 'tndards (lb) a- ':.-il as the optimumi size

c.f sil*c el to be usie (17), 'te proceo.ure used is

sl! il-ar to t-.ut of air, .we.%t:.ian .in- ,:os.:inri (18, I.) for

t..e re.a ration .- f .:-as-oil (n1 :vw x t'r:-.cti.-ns of petroleum..

,i1:;ost any prclar liuid V.'LICn does not r -ct -.Itn the

hydrocarbons, the a sorbent, or tle material of the ad-

scr. tion tube ,i.-i: be used to il.splace tie :,ydrocari on

..atrrliA. it i'; also detirr.ble t'.nt th'e i!e-orbing liquid be

cu ,,lAtely sol.:blc. In water an.d profe'-entinlly less soluble

it tie hy.rocaroon, in orler t-."t its re-ioval from the hydro-

carbon ,nay be ror iilv: cffecto by extraction with water (16),

bLer na.ily 1]isi.laceo ti-!e rro-iatic hvdrocarbons but they

r ain 'hjtria. *i -' within ." e :;icro.rco 1c 1 t. Ln st Ces I.i the










adsorbent. For these reasons the Brureau of Stondards

recommends that methanol, ethanol, n-hexanol, or

cyclohexanol be used as.displacents (16, 19, 19). As the

desorbed material issues from the bottom; of the column,

it is separated into samples of approximately ; c.c. each.

The refractive indices are determined on each of the

samples and are plotted versus the amount of liquid

collected. From this adsorptogram the amount of paraffins,

na;'hthenes, and aro:.iatics may be determined (1i).

Fortunately, the breaks between various plateaus on

aAsorptcgraris for petroleura distillates are -eierally

sharp, sr'owini.- a reproducibility for t e various groups of

about two per cent (5). The separation r'ithin t:i( aromatic

u:roup of !nonocyclic and dicyclic courmpounds may be sufficiently

,;ood to per-rit individual estimation of tiiese classes (7).


B. eosulfurization i otiiod

C, rOview of the literature in regard to the desuliur-

izaTion of ;,a oil by hydro,'enation revealed that the only

process on which comrpreihonsive data have been published

uses a cobalt-mobybdena catalyst (11), The oil to be

processed is fed to a suitable prehea:ting zone, mixed with

hydro-en ani tnen passes over the catalyst. Conversion of

the sulfur compounds to hydrogen sulfide and hydrocarbons

occurs either in the liquid or vapor phase. The effluent

from the reactor passes throuw-l a cr-ndenser into a suitable











syste:,- of ras-so .arators and product receivers. The liquid

product Is freed of hydrogen sulfide by caustic washing

or distillation.

The operatlnr conditions used for desulfurization

depend on the crnaracteristics of the stock being processed

and tile 'ogree of desulfurization desired. Usually the

conditions are in the ranges 600-8500F catalyst temperature,

C.b-lo.O liquid icurl:y space velocity feed rate, 150 .sir. or

more, .ind ,i;th t'- circulation of 1,000 to 10,000 cubic fact

of by iro:on pefr barrel of feed (12),

In excess of 1::01i' li::uid vol:,umes of "'eed hiave been

(cosul'frize-i b- one Vlu 7O .a ,'' cat:lyVst witho;.t re oT.ijration

.,i'l without -.ltoct bl- loss in activity (:). 'i'no catalyst

c'rin be ru,-rneratoe rp,eeiteily to its original a..ctivity.

'-e enerati;:n is acco:qlitshed by controlled oxi-ation to

rei.ove tte carbon, :J3. ultaneously, :,ny metallicc 'ulfl ls

_prsonrt in the' catalyst is co vert,e to oxide. These

reactions ,'enerato a large quantity of heat and particular

care rust be tn1-:on to pr vent local over-eatlnjg of the

catalyst 'Ich 1 -: iit cause shatterinc7, sinterlnz or other

:eleterions clian -es L r-hysical structure (;),

oe- cob.-lt-'.iol"-,-ld-rna c.talvst is made by absorbing

sauttablo cob .t and i.ol-.odenum salts In hydrous or dried

uiu ,ri-is (1), rite copreclpitate '. catalyst i:n prepared

b :id'in' a water solution of cobaltous nitrate to snrrLe

'.oell sti.:.re'n: i i v'ous alu-i.ne followed y an a-n loniacal










soLution of molybdenum trioxide. After washing, the gel

is dried at 2000., crushed, mixed with a suitable pelleting

lubricant, pelleted, and then calcinei for several hours

at 1100oF. Alternately the cobalt and molybdenum salts

may be absorbed in dried alumina pellets or beads, dried,

and calcined.

Cobalt molybdate may be considered a chemical union

of cobalt oxide and nolybdic oxide, CoO.,'oO;. a comparison

of the results of tests usin7 each oxide separately and in

physical mixtures as catalysts reveals that neither oxide,

alone or in mecnanioal admixture, ap'..roaches the activity

of the chemical combination (2),

The mechanism of the desulfurization is not known.

Available evidence indicates that in the case of thiophene

strong adsorption of the compound on the catalyst occurs

followed by hydroenation to thiacyclopentune. The ring

then hydro-ruptures to give butyl mercaptan which miay lose

hydrogen sulfide to yield an olefin. ihe olefin is hydro-

gen.ated to a saturated hydrocarbon (12),

fiendricks, Huffman, iearker, and Stirton (11), have

published results of the catalytic desulfurization of

petroleum distillates which show the effect on the amount

of desulfurization of varying space velocity, pressure,

temperature and hydrogen rate. i'revious work by ryrns,

bradley, and Lee (2) Indicated that in the case of most of









tae coucounds conslderei, 6500FP represented a rather

critical temperature. If the catalyst temperature was

decreased iuch below this fir:ure, there was a rapid decline

in activity with a resultant r:lcrease in the degree of

LI':sulfurization. .i .-ore or less constant dcsulfurization

activity' was txsiited at te.-r eratures between 6500?. and

-00F. .ith little or no evidence of hydrocarbon de-

co..position. :oreever, catalyst activity was maintained

over a mnuch Lornger interval at b50o., to 70O0?, than at

more oluvated temperatures. -'or tLis reason they selected

bt'JOoP. as the :ust desiraulu temperature for operation.

Ihe results of ondric s and associates (11) show that

duoblLr: th feed rate (fro.r 1.0 to 2.0 L.H.-..V.)

a.; roxi .atelyr doubles thc i..roduct sulfur (from O.U15 to

G. 0O Wei .it :.er cent),

-n 1.icrease in pressure fro. 150 to 250 pounds per

sluare bict cu e r-sults in considerably increased de-

s'.lurlzation (fro.a 0.0C6.C to C.&ij, wel..:ht per cent).

increunlinc the hydror-en rate fro'- 3000 to 6000 cubic

foet ,:r !inrrel of ieed caused a small Increuae in r.roduct

sui:ur (rr .m 0,015 to 0.05 weli.-t jer cent) ..,icih was

probulby iije to the dilcrcuse in contact ti.ie of hydrocarbon

'eed aUn caltlyst,

,.- a. oil ch!-,r'.e used in thoir invcstlritions

c',ntai Lied .'.< rnl :;it ;er cent sulfur andJ .as taken fro.i

Anta aria Vullav crude oil in rc,lular refinery operations.










C. Analysis for Sulfur

the method employed for the analysis of sulfur

in the various petroleum fractions is according to

American society y for Testin. V:aterials method of test

SE 0-46 T. The procedure used is as noted under

"Organic lMaterials in -"eneral", The cinemistry of

the :ect!iod is illustrated by the following reactions:

KIO3 + 51l + 6-C1 M 3Io + 6C1l + 3H20

s02 + 12 + 2H'"-O 1 7I04 + 2HI

0.5 S = I











IV. U:;SC :it-TL: U? rr,:r'

A. Desulfurization Unit

ihe desulfurization unit co.nslsts of a feed tani,

licui-' feed rota::ot.r, hydrogen feed rotaneter, foeid

preheater, re:cct,.r, cooler, product ta-k, scrubbers,

and swet ~-s meter to:-et..er
controllers for tihe pre-at.ter and reactor end the

necoa33ary ..rFssur control a ...aratus, A picture of the

ap aratus is s,.own in I-1 ur9 2 and a flow dia'r.Lm in

'_ure a.

the fer.d and product tanks are identical in

construction. 'i'hcy are fabricated from three itch extra

heavy steel pipe und e.-ulpped wit'i Jorgens reflex type

liquid l-vel es'9e, 'he tanrs are 16 inches in outside

len tli inl have a capacity of 200 cubic oenti.-oters, ..'oth

tan'- are wr u.:e.i wit!i a 0.2b 1:-!cn co:. er tube through

*:..iclh stoa-1 is passed to maintain the to:i erature of the

li:,uid at 2000r, ';'he tsn.:s are i slated with Johna-.. ansvillo

asbestos shorts. 'y 'wre hy;,-odrosttically tested at u.O0

pounds Opr squac're InchL -ago.

I'he Li rd fo.' rot amter is a .ch:tte and roortiinr

0.5 .inc:; ur..':ro rti'.tu-ieter .avi n.- n average flow capacity

of 1000 cubic conti-eters ::er hour, It was -!osined for

viscous ;.otrole'iu liqu.idn and is eqiil: aid .*1th three rtors

in order t'at a wide rarn e of viscosities -ny be covered.






























































,,* .....
.. ., .. .
,, .


.. ..... :..


: ..J .. .."


mm** ;
.,.7 i ip


64








?5jl~re 3


*. V-fl*-T '^'.


CAS
I. T-?


" "UL -


DRAWN BY: J -C. ENGINEERING AND INDUSTRIAL EXPERIMENT STATION DRAWING NUMBER
CHECKED BY:
DATE: UNIVERSITY OF FLORIDA
SCALE: GAINESVILLE
REVISION DATE MATERIAL




TOLERANCES UNLESS OTHERWISE SPECIFIED
DECIMAL FRACTIONS


-LY


-. -.'. 1' --










The hydrogen feed rotametor is a standard one-el-'nth

inch Scriutte and Koerting rotameter having: a naximurm

operating pressure of 450 .-ounds per square inch ga;e.

Tne feed proheater comprises two stainless steel

coils 36 inches lonr inmnersed in an oil bath. 'he

hydrocarbon and hy-roren are heated in separate coils

in the same oil bath. They are -ixed toi-etner immediately

upon leavLng tne preieater and the te:p.erature of the

co.-olned street controls the temperature of the oil bath.

'The oil bath is heated by two 500 watt, 110 volt immersion

heaters and its temperature is controlled by a ;.rown

contr-oller.

The reactor is a stainless steel standard A'lrnco

:Super-pressure vessel riodlif'eie to havo a removable head

on each enj and a supt.ort plate on eacic end. .he vessel

is of the 4-3/8 incii series ano has a catalyst capacity

of 2200 cubic centimeters. It is constructed of 16 per

cent chrome stainlessss 'teil, Type 410, and has a maximum

working, pressure of 5600 pounds per square inch at a

temperature of 800'. The vessel in equipped with a

heating jacket contain.irg two 000 watt, 22 volt, electric

heaters connected as shown in iirure 5. sc:ei-iatic

diagram of the reactor is given in Y-'irure 4.

The cooler is made from a 40 inch length of 0.2b inch

stainless steel tubing coiled in a water bath. The water

flow is countercurrent to the flow of 'hydrocarbon.




.Co JL


Catalyst
uprort
Slate -


Thornocouplc
-* .ubo


'ilot


DRAWN BY. ENGINEERING AND INDUSTRIAL EXPERIMENT STATION DRAWING NUMBER
CHECKED BY:
CHECKED BY UNIVERSITY OF FLORIDA
DATE
SCALE: GAINESVILLE
REVISION DATE MATERIAL

131 chrome stainless steel


TOLERANCES UNLESS OTHERWISE SPECIFIED
DECIMAL FRACTIONS


!Figure 1










figure e 5


volt line


to terminals marl:ed
LOAD on controller


........G DlIAG rAIT PC02 1LATI'G JAC:I>T IJITH CC':7.'OLL.R
DRAWN aY: J~ T ENGINEERING AND INDUSTRIAL EXPERIMENT STATION DRAWING NUMBER
CHECKED BY:
DATE: UNIVERSITY OF FLORIDA
DATE:
SCALE: GAINESVILLE
REVISION DATE MATERIAL



TOLERANCES UNLESS OTHERWISE SPECIFIED
DECIMAL FRACTIONS











The scrubbers con'l-st of two 2,000 cubic centimeter

ihrleruneyer flas'cs wi:ich are partially filled with a

cold sodluri lI.:droxde solution. ifter the liquid is

seoarated from, the excess gas in the product tank, the

gas is bubbled t:!rou-:h t:.e caustic solution which

removes tne hydro:-en sulfide form:ael urin:- tho de-

sulfurization :.rocess.

heo wot 'as .-.eter is st.-nJard in design and

construction. .'ter t..e .,as jasses t:.rou-h tue wet

,as zioter, it is bu',ned in a 'ischer type burner adzipte.l

for hydro en .''rnin.-.

-ho feed 11 i.. is. : ..;rce-l tlrou -h the system by

pressure fro:-. a :iitr.,acn o:. -rider, A standard roculator

is uCsd on titn cylinder and a pressure api-,roxilately

five Jounins K.er square 1 cli '.iher tiLan the ro,.ctor

pressure is .i-aintained on tleo feed tank. ihe rate of feed

flow is controllo;i o;, a needle valve between L le feed tank

sn.i t-.n arriorc.d rote 'eter, i'lto fee lines I'fo:m: the feed

ta.k 1 o the e l..ator are steam truce' to provent

soildflication oi' -as oils having ii-h pour points.

'lie reactor :..rLsaure is detorninod by tus pressure

sctti-, c the v e u.lutor V:lve on thOe hyd'ror,-rn supply tank.

'r:-s rc.-u.ator can :,izrtali -elivery pressure up to 1,00i

pount3s ;,er aqutaro Inci! ;:age.

,Th oic : 'ri.. uro on 1',1: .! vnteo is la i.-, ntuirned by a

pressure r *'ulj:tor i th product tillk. 't:s re :ulutor










reduces the pressure from that of operation to approximately

fifty pounds per square inch gage. A low pressure reducer

then further reduces tne pressure to about one pound per

square inch gage pressure.

The rate of hydrogen flow is controlled by a needle

valve on the exit of tne low pressure regulator.

The reactor contains 1,800 cubic conti.ueters of 7.5

weight per cent cobalt-inolybdate supported on .-ocony alu.-ina

bead catalyst.

B. Adsorption Apparatus

The absorption au..aratus shown in Figure 6 was made

according to Burenu of SJtndards specifications (17). The

column has a packed section 1:50 :nill.iieters in length

having a ca:,acity of approximately 160 r..ras of silica gel.

It is supplied with two receivers with ca;.acities of 6.5

millilitersrs and 10.5 milliliters respectively, !graduated

to 0.02 milliliters with 0.01 milliliters esti .ated.

Tie top of the reservoir of thVe ccluin is connected

by means of a spherical :round joint to a nitrogen

cylinder regulator. A cylinder of nitrogen is used to

suy,.ly the pressure to the column necessary to maintain

a product collection rate of seven to thirty milliliters

per hour.

The adsorbent used is Davison silica gel with a

.article size range from 2: to 200 mesh. It is necessary

to use a fresh silica gel charge for each adsorption run.




a,


.-igu h 6


A&do n C olumn 1


r?
It~E~:
:~E~~


IF










V. ,\.OC_;OTJURE

i. Desulfurization A.pp ret.is

:.11 valves on- the equipment are close. '..'wo thousand

nilllllters of the oil to be desulfurized are charged

into thl feed tank. ':'he 7teai. to the heatin-, coils is

turned on ."n the oil allowed to reach it- equilibrium

teni;erature of ,p- roximatelv Or.0,'.

Th.: heating. ulnts of the ri ctor anR reiuot.er are

turned on -.nd the ter.iperature controllers set at 700F, .nD

30OP. respectively. :A'ter t:iese t,:mperatures are reached

the equipment is ready for operation.

One t.rousand milliliters of a :'0 :er cent sodium

hydroxide solution are put into each of the scrubbing flasics

and the water level in the wet --n *eter is filled to the

correct height.

The pressure regulator on the nitro-en cylinder is

adjusted until the pressure on the feel tank is a... roximrately

205 pounds per square inch gare.

The pressure regulator on the hydrogen cylinder is set

to deliver hydrogen at 200 pounds -.er square i':ch cage

pressure and the needle valve between the hydror-en regulator

and rotameter is slowly opened fully, Ihe regulator Is ien

adjusted until the reactor pressure .-ba e read 200 pounds

per square inch.

The hydrogen flow rate is adjusted by vreans of the

needle valve on the exit side of the low pressure regulator











until a l'iow rate of a'boit 24 cubic feet per hour is

idlicated on the roLaneter,

The liluii feed rate iso set at BOJ miillliters

peo r hur by :;i:ens cI' tiLe needle v:-.lv between the feed

tank and ar:.iore.i rota..ieter.

A wet gi;As meter reoi-in,- is tal:~n as the liquid

feer.1 !s intr'-duceJ. Tnc to-orerature, flow rate, pressure

un,! wet gas neter re,! in-s cr- recordeJ at ten minute

int c v- 1ls.

l-ie hydro-en :7as fro. the wet '.is a.eter is fed to a

burner and burned. If necessary t..e water to the cooler

::..-'y be 'urniis on. in tn- case of *:as oils having, '!i:-h pour

points care must be ta:.en tiht too lo. a to:n-.erature is

not mnainalned.

Ti. or, tL i co:-.clusion of t.h run tr.o bydroon re-ulator

anid liquid feed c-ntrol VLIve are closed and the heating

units tLrnod off, After th-e .resure of tnie s:,rstemn ias

fallen to at .c.silieric, t ic ;Prouct Is re invel from the

ir-',juct tank t7 reoovin the 0.5 inch pl:je plur from the

botto:ni of th tank ind lthe inount cf product is measured

bnd recurdei.

Si; :-'c'ro- .ure is for a U1-Iu ho r spacO velocity

(L. .. .V.) fi' .5, a 'i'-ro en feed rate of 4,0t.c0 cubic

feet (,,rr .ir r barrel of .-ro.luct, an avera:-e reactor

te.. erS.t'.re of ,ubUo ''., ;.:! a reactor Lrea-sure of

.:LL ounds er square 1 c' ::a' e.










B. Adsorption Apparatus

The adsorption column 1.3 filled with silica gel

and packed by tapping throughout its length '.ith a ruo .er-

covered wooden rod. The packirig is continued until the

level of the silica .:el decreases less than five 1.illiliters

in five minutes of packing. Sufficient silica tel should

be initially charged so that the final height of the

silica gel is about two to five conti-eters below the

bottom of the reservoir, .*en filiLin' tihe column vith

silica ;el a continuous flow should be maintained. .there-

ever the flow is stop aed, a ring will appear during the

adsorption process, while the ELureau of Standards procedure

makes no iuention of this effect, it was thou .it desirable

to keep the formation of theso rinns to a 'nlnimum.

After pac.ki.:, 100 milliliters of [gas oil are introduced

into the reservoir, care bel-..> taken not to wvet tae upper

portion of tihe reservoir, pressure of f'ivmt to ten pounds

per square inch is then applied. lfter theo sa.:ple has

completely entered the silica eel (about 40 to 60 minutes),

the pressure is reduced, the reservoir opened, and a layer

of two centi:aeters of silica -"el ad:ied. The reservoir is

then filled with1 ethanol or n-hexn.riol uni sul'ficient IpressLre

a.-',:lied to rive flow rates between ten &nd thirty milliliters

per hour, .hen a fraction 'Las collected in the receiver,

tre flow from the adsorption tube is interrupted by closing











trio stopcock. Forty seconds are allowed for the upper

!..arts or the receiver to drain before the volume is read

and an equal interval ullov:ed for Irainage after the

withdrawalal of the bulk of the fraction before the stopcock

on the receiver is closed.

Joth et:ianol and n-hexnnol were used as desorbants

during the course of the investi-ation. ."thanol is

preferred because it is more easily separated from the

hydrocarbon than n-nexanol. It is necessary to completely

reo.rove the desorbant before sulfur deter:.inations are made.

The othanol was easily reaoived by placing the sample in a

steam batn for a two hour period. To remove the n-hexanol,

it required Leriods up to 24 hours.

,ifter com:.letely re,-oving the solvent, the volume

of hydrocarbon rc:nainini." was r.eanured and its refractive

iriLX deter:miTr;e--. T.y plottlnc refractive Index versus

percent of saj.i.le tiinu.-h the adsorption column (percent

und .n1. -:-re equivalent in this investigation since

10'. .1. S&.-les .ere usel), a series of points are

ontiauind. 'i'Trou,-.i t:,ose points a series of tlrooe straight

lines can be drawn, e-chi havtin, a different slope (see

r'i -ure 7). '.'ie Intersccti.-ns or the center line with nach

of tUe other llr-ins i-notes the oroak points between the

:.uri nll'ln in. i nu.'I, thon,- un-1 ;i-:.J-p then nn-' aromatic fractions.

his ..et;.od is essentially t'o same as that reported by

.i.r :.nl iorziati (lb).




t .. .1 :... 0: .. '. ; .

* .: .













9.* ; O .
1 520




1. 50

" ". 0


,^ ^ :* ,' '
















.-1480






1,470



. ..* : .



tc .* *


50




Figure 7
Typical Refractive Index Plot
Sample 8-100-F at 40 G.


20 40 60
Per Cent Through Column


A 4 ;
.%- *
41 .dt* -











;iefrIctive iinices were determined at 250C. except

for those samples -ihich were not liquid at this temperature.

Por sa .ples ziav[inr, pour .olnts above 2?0C., the refractive

indices were ensuredd at 40C0

The ze,.aratlin between paruffins and naphthenes was

ver;7 s..aru in tPhe case of samples containing no sulfur

in tii.e :ar:iffin fraction, the point of change could easily

be seon. The &.arafi'n fraction was water white and the

ri.- .at.ene fraction .lee:-ly colored. The sliarp change can

be soon in iL.-ure B. Tno sample on th.e extreme left is

te urL-i:ial .-as oil used as feed to the adsorption column.

-ecause of wL.e dark color of both the na;o-ithene and

0iro autic portions th;e break point could not be

doteLr.irncd without th:e aid of the refracto.ieter,


C. Sulfur Analysis

''lie sulfur analysis was performed according to the

instructions <-iven in knerican societyy for Testnin

lautoriils test miet:hod 30-46 T using the equipment

I..nufactured by the Ltboriotory :.quipmont Company.


























Figure 8

Adsorption Analysis Fractions
Sample G-152
:*!. .,. ^C *; _'i .- ..'..::.-...^.: ***. ., ..,,- ., .. ..


- r .r --


At










D. experimentall Data

a total of eipgteer.n ras oil S iAples 'rom nine

different crude oils :tire obtained from oil companies.

The crude oils from vnich te gas oils were cor.Lercially

s-juarat-ad 'eg'rcs-3nted ni-ie separate reo raphical locations.

becausee of the difl'erent r1as oil a,.eclfications existing

a,.onr the oil co-.:panies supplying the samples, it was

possible to select only one set of samples having the same

viscoiaty andi *rrvity characteristics.

Since trLe purpose of tl.is invest action was to

deter:.iino teic effect of crude oil source on tihe catalytic

dosulflLrization uliochanisn, the samples sere selected so as

to :ive all physical characteristics as nearly lientical

as possible. In addition, one sample havingg a somewhat

different viscosity and gravity was desulfurized to see if

un.- change in dosulfurization 3ue to physical properties

was indicated.

Also three additional ,.as oils of widely different

pii;sical ciLaractbristics wore separated into fractions by

-aiBsrption to oetor.:ine tnhe effect of viscosity and -ravity

on com;,osition ani ';r.ulfur distribution.

The catalyst used for t'ij:: dosiulfurization was selected

because .!ir,- ;ubl'l.cI nlrtrnoation wa:i ;vuilable on catalytic

d',9u.lfrizaLion ai::!l..: a cobalt-nwiol, lona Ctitul'St than any

otnier k-:ind. I'ho te::iorature of thU dosiilfl'rizat ion reaction










was shown by Burns, bradley, and Lee (2) to be rather

critical in that temteraturrs in excess of 7500F,

caused excessive cracking of the oil and coking of

the catalyst while at temperatures under 600F. the

rate of desulfurization was very low. An average reactor

temperature between 6000F. and 7000F, was selected for

use in this investigation because it was recommended

by the above mentioned authors as being overall the :most

desirable.

In com.::ercial installati ns, low-pressure operations

are those r.'nich are carried out below 250 psig. To

operate at pressures in excess of this requires the use

of more costly equip:nent. Because it is desirable to

operate at pressures below 250 Y'sig. for this reason and

at pressures above 150 i'pig. in order to obtain a

satisfactory reaction velocity, the -edlan pressure of

200 psig was selected for t.lis investigation.

The liquid space velocity and hydrogen rate were

chosen to conform with those reported by iuffran (12).

The oils used in this investigation received no

special treatment except for washing with a caustic solution

to remove free hydrogen sulfide before adsorption and

leterraination of sulfur.











VI. HI-SCrTS

iLie desulfurization apparatus operated very

siootlily arn' the runs w.re nade at essentially constant

conditions. It wa3 found that ti o :h:;dro-oen flow rate

coul--. be~i more easily deterr-ined >'y the wet ras meter

t'r.an b,~ Lt-ir h-rro. on rota-.eter, 'ue to hydrocarbon

vua.ors in th!e .as ti:c rotor tended to stick in the

rota-. eter tube ar.d the rotor level Cluctu-ated over a .ide

ringe. Use -f a o1.:: pipe clean r to clean the rotu:..eter

tube thoroughly before each run reduced ti.is trouble but

did not co'.-ipletely overcome it. i-'ortunately, once the

flo,' rate was set it remained constant during; the run so

no operating: trouble resulted,

In t'he case of the Florlda oil, s:-.-aple nmer S-10-',

t..e color was so dark that tile rotor level could not be

jeteriinei once i1te outer portion of tan rotu:,.eter tuoe

wus filled. 'iTho flow rate woo adjusted wIile the outer

portion was beirL. filled .n! nrc t'urt''er chan.(es were

nfecesarj,

rhe ,-as flow rates ire letorni ned u;.on the coi:;pletion

of le run Lby ,ans of the wet -*ns peterr readings and tihe

Icn tu, of the run in the case of il,:dro:ren and by. measuring

tu:e feo-! re:-.aunnI r,. .nd tieo product r2eeivei in the case

of tioe ,'us oils.










All runs were made at a liquid hourly space velocity

of 0.5, reactor temperature of 6500F, rnector pressure

of 200 pounds per square inch gage, and hydrogen feed rate

of 4,000 cubic feet per hour per barrel of fresh feed.

The results of t:i', desulfurization runs are shown

in Tables 2 to 4. An examination of the data reveals

that in every asaiple, both before an-1 after desulfurization,

tie per cent sulfur is greatest in the aro-matic fraction

and least in the paraffin fraction. This is in accordance

with the .present theories on the subject and tends to

substantiate them.

A survey of the amount of sulfur in each of the

fractions, both before and after desulfurization, shows

that the sulfur contained in the paraffin fractions is,

in ,general, 'iore easily re- oved than that in the aromatic

and naphthene portions. howeverr, all of tie sulfur is

not r'c-moved from the paraffin fraction before de-

sulfurization of the aromatic and naphthLenic fractions

begins. Desulfurization appears to occur in all fractions

simultaneously with the rate of desulfurization being

greatest for the paraffinic and least for the aromatic

type of sulfur compound.

In every case in which the sulfur content of the

paraffin fraction is shown as O* weight per cent, the

fraction was water white in color. In the case of sample

G-129, the paraffin fraction before desulfurization






37


o4o o










m O OO N t ON 0 t 00 -4
> N rN




1. 1. ID 0
0






S .
** 66
C- M 0 00\4H49 40O







0 0(1 0Y 0- V~r t o 00
0 0










S o to W .

,.. a 0 O,- .. 0 0 0 0 r r4V




0N
E a m 0 N I ra

o to
0 r 044 t rl- < e (
toi I* e o & a I

"m


1 '0 0 Q1 -t 100 ID 0
o. 4 5
rj A 0 0 QO Te Q
-4 n V4 C m r-4 M c LA

0

2m 0



1. g Inr-

v= ril 0 ** o
tII O 0000 k 4 god
%0. 4NI 00 so 0 r0 00










Table 3


Tabulation of Data on Adsorption Feeds


I G-125 : G-128 : G-154


Source* : Talco : Kuwait : Fullerton

Sulfur, .;t. 0.648 : 1.880 : 2.210

Gravity, o0PI : 24.7 5 31.1 : 25.6
Refractive Index s 1.4973(1) : 1.4R43(): 1,4900(1)
Vis. .. 100oF. t
cp. : .15 -
s.s.u." : 43,8 -
4
Vis. 2100F. a
s.s.u, : 44.5 : 63
c.p. j 5.91 : ; 12,4

:Sp.,r. : I
S100F. : : 0.88 : -
2000F. : 0.854 : I 0.856

Cop:[position s 4
Vol. f | 19 : 44 46
Vol. ,M M : 35 t 21 : 27
Vol. A z 44 3 54 2 27


'data determined by
(1)-efractive Index
(2h)efractivo Index


corpuny supplying sample.
at 400C.
at 250C.












Table 4


Sulfur Distribution in Gas Oils


:Total as


*t
: .t. :
G-121 : 1.6e :
G-1''i-P : 1,42 :

G-126 :0.71 :
G-126-P : 0.56 :

G-129 2.65 :
G-129-1 :1. 0 :

a-162 0.51 :
G-132-i 0.41 :

'3-153 0,55 :
3-13.-P 0,57 :

G-137 : 0.87 :
G-137-k' 0.61 :

-10C-F :., 06 :
.i-IGL-P-r :2.34 :

G-125 i 0.65 :
G-128 1., :
G-134 :. 1 :
S


1,uraffin : Narhthene : Aromatic


Fol. t. :
7 00,58 :
15.0 0.39 :

16.0 0.56 :
17.5 0.24 :

16.0 1.07 :
18.0 0+ :

19.5 0+ :
20.0 0+ :

'8.5 0.32 :
27.5 0* :

1:i.5 0.23 :
21.0 0+ :

27,0 2.58 :
24.0 1.06 :

19.0 0.50
4-1.5 0+ i
46.0 0.84


'I


fol.. ..t. s S
32.0 1.09 "
29.0 0,97 :

39.0 0.59 :
41.5 0.52 :

33,0 2.20
30.5 1.10

.G6.5 0,44 :
35.0 0.33 :

32.7 0.53 :
34.7 0.37 :

30.0 0.64
.0, 0,36 :

26.0 3.40
30.5 2.38 :

35.0 0.64 :
20.5 1.11
27,0 1.62 :
S


Vol.,, V t.1;.
53,0 2.32
56.0 1.88

45.0 0.74
41.0 0,74

51,0 3.36
51.5 2.74

44.0 0.00
45.0 0.60

38.. 0,* 4
37.8 0.62

bl.b 1.17
51.0 0.96

47,0 3.77
45.5 0.04


44.0
34.0
27,0


0.74
4.71
3.20


;oto: "P" in saiple number denotes t,.at
it is a desulfurization proiuct.


I


-^I


--


~ -~-----~~-










contained 1.07 weight per cent sulfur and had a very

dark color. After desulfurization, the paraffin sulfur

content was negligible and the color was crystal clear

or "water white". There were six cases in which the

paraffin fraction was "water white" and had 0' weight

per cent sulfur content. There was no colorless sample

having a sulfur content greater than 0+ weight per cent.

These data give confirmation to the work of Rossini,

Leslie, nener, ;rair, sillingham ani btreiff reported by

Sachanen (20). They found t*iat the "water white" portion

of a straight-run distillate from a nonca City crude

contained no sulfur. This indicates that when the paraffin

fraction is colored, it is due to sulfur compounds present

and that a lack of color indic-.tes a sulfur-free fraction.

In Figure 9, the weight per cent sulfur after de-

sulfurization is plotted against wei,-,ht per cent original

sulfur. A straight line pasu inc through the ori-:in can

be drawn through these points indicating that the source

of the gas oil is not a factor in its degree of de-

sulfurization by low pressure hydrogenation using a cobalt-

molybdena catalyst. The line drawn between the points has

a slope of 0.725.

The weight per cent sulfur after desulfurization is

plotted versus wei-ght per cent original sulfur in Figure 10

for each of the gas oil fractions. In every case a straight

line results, but the slope of the line is different for














^* ^*\ rf
S. ,^ ,--i *
* ," '*'*
,-- :../: '.. .,
. : ;:: :


: "
7 ": :-./; '-^ ,,



.. '-
.t.

." 5 ;%
.' __ "* ../ .* ^*- ;
,^ .. .. ...


A .. .
--.; V
,- :" "





i's
*. :. *. -'.- ...












4, 4 1,-
*" ." ., .-' *
.% .... '"








- l ,;. .
S '. .' {






.'. :
.. '--':








*^...y^. ":***' ;. ....o'
I :- ..;. ? i.; ,
'j' ,,.



;',' ^ ? '

"' i '"* .<.. *




"r '. *

; --- ^ ." ^ ,
*'*.-* ^*: -A^


1 2 3,
wt. % Sulfur2 1 Pw(n4l,,
IA*


Figure to

Desulfurization of
Gas Oil Fraction .
Legend:
Paraffin
A Naphthene
B Aromatio


Area i -
-F^

_______ -


Ipil
F
r -


rA


3










II
1




0


46-wnsm










each fraction. For the paraffin fraction the line has

a slope of 0.80, for the naphthene fraction a slope of

0.68, and for the aromatic fraction a slope of 0.43.

perhaps the only significance that can be attributed

to tiiese curves is that the greater the slope the more

difficult the sulfur is to remove.

Graphs of the type used by Hughes, Stine, and

Faris (13) are given in Figures 11 to 20 for each of

the gas oils used. A plot of sulfur content versus per

cent through the adsorption column is shown. This gives

a graphical representation of where t:,e sulfur in each

fraction is located and its degree of removal.

The samples of oils from the various sources used

in the desulfurization runs were, in general, selected

with the same viscosity end specific -ravity. The object

of this type of selection was to have oils from different

sources having similar physical properties. The oils

selected for desulfurization were from :est Toxas, Kuwait,

Columbia, Venezuela and Fullerton fields. Two oils

having gravities very close together but greatly different

viscosities were selected from the F'ullerton gas oils to

determine the effect of viscosity on sulfur distribution,

In addition, a third Fullerton sample with a different

gravity and viscosity was analyzed to determine the

variation in sulfur composition among a range of oils















'Fi ure 11
Distribution of -ulfur in C.a~-le G-121
(Gas -il from '.'est To::as Crude)








Bofor .'-c ullu rzati.,n




After -czulfuri ation
r-- ------- -- -- ---
Total






















n
0 ____ _______ --------- ----


: cr Cent bTirou.li


6o
Colwun


100





Figure 12 .
1.0


o0.5


0 I-
0


Figure 15.
1.0,


0


0


Sulfur Distribution in Sample G-126


20 40 60 80 100
.or Cent Through Column


Sulfur Distribution in Sample G-132


40 60
Per Cent Through Column


100


-- <
(sfl r
- i ____-------------


Originally






Figure 14

Sulfur Distribution in Sample G-129




Original



Total __. A tqxl ej


I
I







---_ _-*

^


100


Per Cent Through Column

Figure 15
Sulfur Distribution in Samole G-133


I










S20 40 60 80 10
Per Cent Through Column
Per Gent Through Column


0


3.0





1 2.0





1.0


0


0.7


0o5o





i0.2$


0
E


T T1 T


Orizgirna


rized


iiDesufu


I


II-'





Sulfur Distribution in Sample G-128


4





-3.









1


Firmure l7im


Sullur Disti'ibntion in ?mini~e fl-i 7


Per Cent Through Column


T tal










)20 40 6o0 CO 100
Per Cent Through Colurm


Or! ginal



Total




r------

_____,


160




4 05





0


100


Figure 16.





Picure 18
Sulfur Distribution in Samnle S-100-?
L (Gas 0il fror Filorida Crude)


Original




Total -


Dosulfuri oed
3


I I







02



0
1
0I
8 2 ----------------



0 ,


1 -- J--------------







0 -----------------------


. er Ccnt r. ug c Column


1t'LU






Figure 19
Sulfur Distribution in Sample G-134
(Gas fil from Pullerton Crude)


Per Cent Through Column


Figure 20.
Sulfur Distribution in Sample G-125
, _(Gas Oil from Talco Crude)


40 60
Per Cent Through Column


100


1.0





0o.5





0


I 4 4. I 4


Total I rf


.1 .L


"I


--


Tota











from the same field. A heavy Talco and light ruwait

were also analyzed to determine the sulfur distribution.

It was found that for all of the oils with similar

,.rLvities an- viscosities the composition, v.ithin

reasonable limits, was the same. For example, the weight

per cent paraffins was in the range 15 to 20 per cent,

naphthenes from 30 to 36 per cent, and aromatics from

44 to 53 per cent. In the case of the tree sar.iples

run on Pullerton .,as oils a plot of viscosity in

centistokes versus weilr-ht per cent gave straight lines

for each of the fractions (Figure 21).

lor two of the virgin ras oils analyzed there was

no arprcciablo sulfur in the paraffin fraction. In every

other case, the iitlher the specific gravity of the gas

oil from a :iven source the greater the weight per cent

sulfur in all the fractions, In the case of the oils

having_ no sulfur in the paraffin n fractions, the densest

of L:.e two oils from the same source had less sulfur in

t!.e aromiatlc fraction even though the total sulfur content

of the theavier Y'as oil was .hlirher. There is no apparent

exZuLiiAuotion for tiis but it s'ay be due to an effect the

suliur contont of a molecule has on its a.isorptivity,

The determination of this effect has been made t!he

purpose of another invost:igItion.





I I


101
N.ap,, e -










^ i .-

n *






10---------------------- ----


--------6 8 1'

Viecoe t pb oentlatolks
't d06 F. .


i





*e~ -, 1"
'*' ^ -'


_______ .^ *
---- ----------- ( -- ^- .,
I '~. ''^
^ '' ..^ -


F.







It
*:^

* *

I:


.,





t 5

'. ,

i ':'.'
'u;'",: .d '









.A ..- .' *."
''



.'* .*; ,
'* .- ~, ',





i -i> ^r'- '' ''*.


.4


Figure S


Variation of Gas Oil

Composition with

Viseesity

(FPllerton Gas Oils)


^[ [4i


k7l


B-. *: ^ *'** ;; .. .; *1.. % ? -
.. .. ..... '- ...... i. ,^ '. : ':
.'., ." ._ .. :- .

5 0 '. ... ^.."

". i '" .



''
'."
; .-
*1r~

S' .


**:"./.

.. '*- ,







l.e
'1 .1'*
1 51







S- Figure 22
..*. Variation of Gas Oil Composition with Viscosity
Fullerton Gas Oils at 200P





80 Aomat aos




J 60 -----___---- ---- --------









80
SO0 J^ /------------------






Paraff .ns




2 4 6 8 10 12 14
Viscosity, centistokes











VI. CONCLUSIONS

Based on the data obtained -uring this investigation,

the following conclusions are drawn:

A. The aromatic portion of the rFas oils has

the highest sulfur content and the paraffin

fraction the lowest sulfur content.

B. The sulfur in the par.-ffin fraction is

the most easily removed.

C. Sulfur content reduction occurs in ::1l tree

r&otions simultaneously.

D. The complete r;-ioval of sulfur gives a

"water-white" paraffin fraction.

,. The source of the crude is not a factor in

EL'e low pressure desulfurization of a .as

oil wtien a cobalt-molybiate catalyst is used.

W'. G}as oils lnving the same viscosity aun specific

.-revity contain ap roximately the same amount

of ,araffins, naphtn-enes, .nd aromatics. This

indicates that viscosit-r an' r-rvity delineate

composition.

G. In the case of gas oils from a i-llerton crude,

the amount of each of the molecular types present

(i.e. paraffin, naphthene, and aromatic) varies

linearly with the viscosity at 2000F. in

centistokes.











VII. :LIBLI D:0R,.1iHY


(1) Ballard, ;. F., irritt, N. A, and Oosterhout,

J, C. D., In'. :ng. Chem., 41 2056 (1949).

(2) Byrns, A. C., .,radley, ,. :., and Lee, iA. '.

Ind. j;n,. Chom., 35, 1160 (1943),

(3) Clerc, H. J,, ilncannon, C. : ,, and ier, T. P, Jr.,

.anal. Chem., 22, 864, (1950).

(4) -,ole, r. i., iAnd Davidson, ,. G., Ind. -.nr. Che:rm., 41,

2711 (1949).

(b) Dinneen, ., U,, Tihoison, C, J., :Mith, J. :<., and

.all, J. .., .nal. Chem., '2, 871 (190).

(G) Furby, ,. ., final Chem., 22, 876 (1950),

(7) 'oo!lin;, i. i., :,n.i .opkins, i. L., ppier presented

before bivlsion of letri.leun Chemistry at 110th

..!eetin 'tm. Chem. LSoc., J-icago, Ill., eQ;.t. 1946.

(i:) .;ilnes, ,, en> er, J., ::elm, '. V,, Lnd Ball,

J .., U. :. iur, lines, se .t. Invest, 4060 (1946).

(9) :..:lo, T. -.ir. .:ons, .' C and *Eisenhunt, P. F,,

i.. l.n~. Jltoem., 41, 2702 (194.).

(10) A rlin, *. V., :a ies, ., .n all, J .i. '.

-ur, i.nes, Rept. Invest. 4566 (1.49).

(11) 'cndric.s, :, ., ifuff:.nn, :. C., turker, R. L., Jr.,

.l.J ti.tr.jn, ti. I., ri,:r.er pr.-serlted before division of

ietrleu Ch-onistrv at 100th i.'oetinrw, -m. CLhem. Soc.,

:tlu1ottc City, ., J., %,pril 1946,










(12) ![uffman, H. C., paper presented before the Southern

California Section, .i,. Chem. Soc., July, 1949.

(13) Hughes, .. C., Stine, H. i., and P'aris, ii. i.,

Ind. Eng. Chem., 42, 1879 (1950).

(14) Lien, A. r., icCaulay, D. ,,., and :vering, i. ,,

Ind. Eng. Chem., 41, 2698 (1949).

(15) iair, iB. J., and Forziati, A. F., J. :es--arch Nat.

Bur. Standards 32, 1L.1 (1944),

(16) Ibid., 32, 165 (1944).

(17) Ibid., 34, 435 (1945).

(18) Liair, ib. J., :'-aboriault, A. L., d:. :iosslnl, F. u.,

Ind. .ng. Chem., 39, 1072 (1947),

(19) iWair, o. J., Sweetman, J. J, and n :ossini, '. D.,

Ind. .n,. Chem., 41, 2224 (1940),

(20) 6achanen, ... N., "The Chemical Constituents of

ketroieum", Reinh-old :ublis'hin7 Cor,.oration,

;:ew York, (1945),

(21) ochweyer, H. ',., and -.dwards, C. H,, "An .valuation of

Sunniland Crude petroleum", Florida .n.ineering and

Industrial ':xperiment Station Bulletin, *t-'.ries .!o, 27,

,.ay, 1949.

(22) Seyfried, ,. D., Chem Eng. News3, 27, 2482 (1949).

(23) S;nith, H. 1., and Blade, 0. C., et. ;ef., 27, 5, 101

(1945.).

(24) Vorhies, Alexis, Jr., and Smith, M., Ind. :.ng. Chem.,

41, 2708 (1949).































IX. Ai' :;iDIX











Table 5-A

Tabulation of Desulfurization Data


: Time : Peed : Reactor :Reactor: et Gas ;.eter
: in. :Roteaneter: Inlet, : psig. :Cu.Ft. 5F. in.h20


G-121 : 0 :
S10 :
Rotor .73: 20 :
0.2 gm : 30
: 40 :
: 50
: 60 :
: 70 :
S80 :
: 90 :
: 100
: 110 :
S120 :

G-126 :
S10 :
Rotor ,12: 20 :
0.36 : 30
: 40 :
: 50 :
S60 :
: 70 :
: LO :
: 90 :
: 100 :
: 110 :
120


$. 'Jig


240
245
245 :
240
235
235 :
245 :
235 :
246
249
243
243
249

151
155
150 :
151
150
14 :
150
143 :
157
148
148 :
156
149


650
500
460
480
490
495
480
490
480
490
490
495
495

700
590
550
545
550
550
550
560
55
560
560
560
555


: 200 :340.0 80
: PO' : b6,.0 G
:200 :369.0 80
: 200 :373.3 80
: 200 :377.8 ~-0
S20o" :531.9 i0
: 20C :3t66.0 SC
: 20 :390.0 ;0
S OC :593. 9 b0
: "rO 397.8 78
: 20, :401.7 78
: 20C :405.5 78
* 200 :410.4 78

: 200 :49.6o 81
S200 :o05.3 -,I
: 20; :11.2 81
: 2.0 :516.5 81
: 200 :b21.2 81
: 20C :25.5 81
: 20. :o30.4 81
: 200 :535.4 81
: 2'0 :.40.4 81
: 20U :545.3 81
: 200 :550.2 81
S20(. :554.9 81
: 200 :559.3 61


0.2
0.2
0.9
0,9
0.9
0.9
0.9
0,9
0.9
0,9
0.9
0.9
0,9

1.6
1.7
1,7
1.7
1.3
1.2
1.5
1,4
1,4
1.4
1.4
1.4
1,4











Table 5-B

Tabulation of Desulfurization Data


: Tine :
S.*In.



;-1.?a 0
: 10
ot or 6: 20
G.z m : 30
S40
: 1 :U
6(;
70 :
: r' :
CO
1 00
: 110 :
: 12( :

G-1L.2 : 0
: 10
.otoLr ;:' 20
0.36 r;.n 30
S40 :
50 :
O 60
70

S90 :
100
S110
: 120 :


Feed : actorr sectortor: et 7as .eter
Aotameter: inlet, : sig. :Cu.iPt. OF. in.m..o


."b'50

23C
245
230
240

242
242
':42
239
242
'-)45

15 U
158
157
14U
139
145
144
135
135
141
144
140
137


dC,

:j50
540


550
560

560
560
560


700
58-0
545
540
545
.A45
545
350

560
560
560
570


200, :424.4 75
: 2C0 :427.6 75
20. :431.0 7o
S20. :4354.' 75
: 20( :439.6 7u
: 200 :445.0 75
S 20' :449.1" 7b
: 20- :403.6 7u
:200 :457,9 76
S 20f. :461.' 76
: 200 :4u6.6 76
S200 :470.6 76
S20( :475.5 76

20j :57.5.b Ul

a 5Cr :5-0.4 81
: 20C :5.6.0 81
: 200 :591.4 81
: 200 :536.9 Hi
: 00 :602.3 81
S200 :607.9 81
S20C :613.7 81
: 20( :618.3 81
: 200 :622.5 81
: 20L :26.6 81
I 2C0 :630.7 81


1.7
0.93
1.0
60.
1.5
1.3
1.1
1.2
1.1
1.4
1.1
1.4
1.6

1.2
1.2
1.3
1.4
1.4
1.4
1.4
1.5
1.b
1.2
1.1
1.1
1.1











Table 5-0

Tabulation of Desulfurization Data


: Time : Feed a Reactor :Reactor: .et Gas ;.eter
: .in. :Hotamneter: Inlet, s psig. :Cu.iFt. OF. in.H40
: t : of. i :


G-133 : 0 : 170 : 700 : 200 :714.5 62 1.4
: 10 : 174 : 620 20r :716.8 82 0.6
Hotor j2: 20 : 165 : 580 : 200 :722,4 82 1.4
0.36 gm a 30 : 127 : 600 a 200 :72;.4 82 1.4
: 40 : 155 : 590 : 200 :734.7 82 1.8
a 50 : 149 : 605 : 200 :741.2 82 2.0
a 60 : 155 : 610 : 200 :747.0 62 1.6
70 : 151 : 610 : 200 :752.6 82 1.5
: 80: 149 : 610 : 200 :758.2 82 1.5
90 : 154 : 610 : 200 :763.8 82 1.5
: 100 : 156 : 605 : 200 :769.5 82 1.5
110 : 154 : 610 : 200 :775.6 82 1.6
:120 : 150 : 610 : 200 :760.4 82 1.6

G-137 : 0 : 78 700 : 200 :641.2 82 1.2
1 0 : 64 : 640 a 200 :644.8 82 0.9
Hotor .2: 20 a 70 630 200 :649.7 82 1,4
0.36 in : 30 : 80 : 630 200 :654.9 82 1.4
: 40 : 75 : 610 s 200 :660.2 62 1.4
: 50 : 75 : 620 200 :6,5.5 82 1.4
S60 : 89 : 610 : 200 :670.7 82 1,4
70 : 76 : 610 200 :675.9 C2 1.4
80 : 86 : 610 : 200 :661.0 82 1.4
: 90 : 71 : 610 a 200 :686.0 82 1.4
: 100 a 80 a 605 : 200 :690.8 62 1.4
: 110 : 83 590 : 200 :695.8 F2 1.4
: 120 : 79 : 550 : 200 :700.8 82 1.4











Table 5-D

Tabulation of Desulrurization Data


: Timo : Feed : Heactor reactorr: ..et las 1.eter
: ..n. H ota o t er: Inlet, : si-. :Cu.l't. uF. In.hl .



-l1O-F : 0 : 20 : 700 :200 :[92..5 67 0.9
S10 : 2;:0 : 570 : 200 :R98.5 67 1.7
.iotor w2: 20 : 570 : 200 :.04.6 67 1,7
0.36 i 30 : : 570 : 200 :910.6 t.7 1,7
: 40 : 560 : 20( :916u. 67 1.5
: 50 : 570 : 200 :922.2 67 1.7
60 : : 6u 200 :927.5 67 1.0
: S S











Table 6-A

Tabulation of Adsorption Analyses Hesults


Sa:rple : G-121 : G-121-P : -16 : -126-
No. : : No, :


1 : 5.22 1.491 : 4.92 1,483 : 5.0. 1.500 : 4.86 1.477
2 1 o.30 1.480 : 4.90 1.471 : 6.30 1.437 : L.12 1.474
3 : 5.77 1,474 : 5.08 1.467 : 5.24 1.495 : 4.64 1.472
4 : 5.20 1.473 : :.00 1,467 : 5.18 1,494 : 4.98 1.473
5 5.29 1,475 : 5.24 1.470 : b.4 1.493 : 5.04 1,474
6 : 5.12 1.487 : 5.00 1.476 : 5.16 1,493 : 5.12 1.478
7 : 5.15 1,493 : 5.2i 1.482 : 5.08 1,493 : 5.04 1.483
8 : o.16 1.497 : 5.04 1,4-'6 : 5.30 1.49 : 6.10 1.4U8
9 : 5.70 1.496 : 5.12 1.41 i: 5.'0 1.493 : 5.50 1.493
10 : 4.98 1,496 : 5.16 1.493 : 5.04 1,493 : 5.15 1.499
11 : 5.22 1,494 : 5.00 1.495 : ..0 1,494 : ..13 1.b04
12 : 4.20 1,497 : 5.46 1.49. : 5.02 1.495 : 5.22 1.507
13 : 3.40 1.500 : 4.96 1,500 : 0.32 1,497 : 6.02 1.507
14 : 3.2 1.002 5.50 1,502 : 5,48 1.500 : 5.16 1.oll
15 : J.3 1.503 : 4,96 1.506 : 5.28 1.500 : ".14 1.10
16 : 4.9 1,506 : .6 1.509 : 3.4 1.500 : E.18 1.508
17 : 3.4 1.512 : 1.8 1.513 : 4,4 1.504 : 2.10 1.50L
18 : 3.1 1.514 : 2.8 1.507 : 2.5 1.504 : 1.3 0
19 : 2.3 1.517 : 2.3 1.508 : 9.4 1.L-4 : 1.V 1.608
20 : 2.2 1.516 : 7.6 1.502 : : 1.508
21 : 1.6 1.51: : 2.8 1.498 : 4.7 1.b08
22 9.7 1.517 :

Total 99.44 97.34 97,7 9i.l10


Note: R.I. 200C.












Table 6-B

Tabulation of .dsorption analyses Results


Sa .le : 0-129 : -1293- : :-132 : 0Q-6!-
No. : :..1. .-.I. : T1. .I. :t :. : Tl h.I.


1 : 4.1
: : v.0
: 44.
4 : 4.9
S : v.0




.0 : 6,4
.1 : 4.*
: 3.7
.L : ..9
.4 : 1.9

LO : 1.7
.7 : 1.4
S : 1.4
9 : .4
0 : .7




, : 4.
6 : 1.
,7 : 1,4
0.44
:9 2H.-

Total rl.CO


4,9igi
5.4.9
3.00
o.07

.05
5.14
5.1b
b.04
o.14
1.11l
b.34
4.'"'






o.3
5.1


1.4528:
1,4501:
1, >-.01:
1.4,.16:
1.4;,30:

1. 486:
l.4L;54:
1.47[:4:
1.4920:
I.. 18i
1. .s>1 "
1.X1'-7:
1.5191:
1,6211:
1.-. '18:
1.:-, 4:
1.5 '53:

J.r'


F.12
5..24
b.OO


o.14
4. F7

J.14

b.17
.. 3'
5.354
4..)0
k.62
3.31
I.bI
1.1
$3.7
4.9
6.0


98.77


1.4590:
1. 4579:
1. 4u74:
1,4574:
1.4574:

1.46L'O:
1.4 04
1.4764:
1.4cr57:
1.4--82:
1.4.10:
1.4926:
1.49-12:
1.4.-0:
1.5C2c:
L..z0,0:
1.50"0:

1. O1u
1..110:
l.,0
lr~i






;


,.00
Li.lu
4. 38
4,U3
b.01
4.b5
0. ".'
5. ..C
5.061
i.'02



3.1
7.3
3.2
2.i
o.b
4.1
4.1


1.4602

1.4o081
1,.4602
1.46 33
1.467'
1. iC7,'j
1.4722
1.4'7 5
1. 47.-9
1. 4-49


1,43.-
1.49.44
1.4@994
1.6012
1. but;'j4
1.4-70
1,4 .'70
1.4:.c9


b96, i


;ote: -.1. "'OC.


1.494
1.484
1.47-
1.482
1. 4 -,,
1.491
i. 4913
1.496
1.401 .
1.49.


1.u j L
1. 14
1.512
1.013
1. ID,
1. )07
I..1.l Oi

1,*.04
1.510
1, 14
1. -17
l.b16
1. ,12
l.b1,513
1.513

1. ;O


--- -------- ---- ----- --~--------- --~----- -- -- -------












Table 6-C

Tabulation of Adsorption analyses Hesults


Sample : 0-133 : G-133-P : -137 : G-137-P
ilo. : il. R.I.'" : 1. R..I. : Ml. R.I. : i .I.


1 : 5.03 1.4930: 5.10 1.4662: 5.01 1.4762: 4.94 1.4611
2 : 5.14 1.4910: 5.35 1.4619: 5.22 1.4697: b.20 1.4599
3 : 5.43 1.4870: 5.12 1.4597: 5.24 1.4700: 5.41 1.4587
4 : 5.45 1.4790: 5.18 1.4590: 5.17 1.4720: 5,12 1,4589
5 : 5.36 1.4760: 5.09 1.4589: 5.15 1.4720: 5.19 1,4620
6 : 4.87 1.4764: 5.01 1.4601: 5.10 1,4814: 5.13 1.4678
7 : 5.22 1.4782: 5.00 1.4658: 5.26 1.4892: 5.02 1.4744
8 : 5.06 1.4811: 5.47 1.4762: 5.23 1.4597: o.14 1,4830
9 : 5.17 1.4843: 5.02 1.4798: 5.11 1.4974: 5.09 1,4889
10 : 4.98 1,4870: 5.07 1,4848: 5.16 1.5004: 4.84 1,4940
11 : 5.48 1.4892: 4.72 1,4909: 5.22 1.5029: 3.43 1.4997
12 : 5.07 1.4880: 4.89 1,4965: 5.60 1.5048: b.04 1.6023
13 : 5.13 1.4710: 4.6 1.4998: 5.29 1.5084: b.08 1.6070
14 : 5.32 1.4620: 4.2 1.5004: 5.41 1.5108: b.11 1,5152
15 : 5.28 1.4526: 3.6 1.5031: 5.32 1.5098: 4,95 1.5200
16 : b.09 1.4443: 2.e 1.5065: 5.02 1.-1,18: .47 1.4968
17 : 8.70 1.4418: 4.0 1.5032: 2.3 1,5158: 5.13 1,4642
18 : 4.98 1.4397: 4.8 1.5025: 3.8 1.6144: 2.7C 1.4591
19 :.? 1.5011: 6.7 1,5047: 1.10 1,4448
20 : : 7.1 1.5002: : 0,90 1.4430

Total 96.76 98.82 96.31 99.06

Note: H.I. 4000, .11 others at 2000.












Table 6-D

jabulation of .dsorption Analyses Results


Sample : J-100-F a S-10')-F-P
No. ;i1. ;.1. I 1. R.I.
_____________:__________


I
S
S
S

a











s

Tot l


4. *5
4. 86
5.13

5.52
Z5.17

8.23
5.41
5.14
5.23
5.48
5.3
.05

3.1
1.6
b.4


1.5171
1.6150
1. 124
1.502c
1.5030
1.5008
1.5022
1.5057
1,5069
1.5090
1.5098
1.5090
1. 113
1.5022
1.5133
1.4763
1,4790


97,40


b.04
6.45
S.* 00
4.99
4.63
4.92
4.94
5.24
4.9-,
4.96
5.36
4.97
. 27
4.90
4.G2
3.1
2.3
3.3
2.8
8.4

37.38


1.4970
1.4805
1.4728
1.4728
1.4747
1,4793
1. 4t73
1,4940
1.5027
1.50c0
1.5015
1.5158
1.U169
1.5190
1.5135
1.5200
1.D200
1.51f3
l.l513
1.51a5


;.ote: R.I.


- --- ----


400,.











Table 6-E

Tabulation of Adsorption Analyses Results


.ample : G-125 : G-128 : G-134
:io. V 1. RR.TI. : I R.I T. R.I.


1 : 5.00 1.5009 : 5.00 1.4510 : 5.20 1.4398
2 1 5.36 1.4783 : 5.16 1.4508 : 5.01 1.4962
3 : 5.11 1.4689 : 4.94 1.4506 : 5.41 1.4960
4 : 5.06 1.4686 : 4.83 1.4504 5.05 1.4960
5 : 5.14 1.4686 : 5.04 1.4504 5.14 1,4950
6 : 4.97 1.4719 :5.21 1.4.02 : 5.17 1.4900
7 : 4.96 1.4780 : 5.01 1.4502 : 5.70 1.4888
8 : 5.06 1.4841 : 5.30 1.4500 : 5.04 1.48B0
9 : 5.05 1.4922 :4.91 1.4539 : o.32 1.4S78
10 : 5.11 1.4922 : 5.05 1.4631 5.12 1.4899
11 5.19 1.5056 : 5.04 1.4780 : 5.16 1.4920
12 : 5.08 1.5090 : 5.08 1,4967 : 5.32 1.4938
13 : 5.36 1.5128 5.17 1.5100 : 5.02 1,4950
14 : 5.10 1.5088 : 6.10 1.5113 : 5.11 1,4983
15 a 8.80 1.5050 : 5.01 1.5120 : 4.30 1.4983
16 : 4.10 1.5035 : 6.10 1.5152 : 4.30 1.5035
17 : 2.60 1.4978 : G.50 1.5158 : 5.10 1.5037
18 t 2.80 1.5274 ; 4.90 1.5190 a 5.00 1.5028
19 3.10 1.b300 : 2.70 1.5223 : 4.50 1.5022
20 4.30 1.5280 : a 2.70 1.5022

Total 96.95 99.05 99.27


Note: "R.I. 400C. All others 200C.










BIOGHArIICAL ITEAS

Jam:es iubert Gary was born .ovember 18, 1921, in

Victoria, Virginia. '.e was 7rnduated from Victoria nigh

School in June, 1938, and entered the Virginia Polytechnic

Institute in September of that year, !ie was graduated

with honors in June, 1942, receiving the Bachelor of

Science in Chemical Engineering degree. After graduationn

he served as an officer with the Anti-Aircraft Artillery

of ti.e Army of the Unite.l States in the South eost i'aocfio

Theatre. Upon return to inactive duty, he entered the

graduate school of the Virginia polytechnic Institute in

october, 1945, and was "ranted the degree i.Vaster of Scionce

in Chemical 'ngineering in je;-tember, 1946. Upon radiationn,

he b1:ecame e;.piloyed in the 'eclnical Service Division of the

Standard Oil Corpany (Ohio) at Cleveland, Unto. In Sept-

ember, 1948, he entered night school at tie Case Institute

of 'ect:nolo>'y and continued his graduate studies there

until Juno, 1949, In Lepternber, 1949, he 'aas ;-ranted a

leave of absence from trie Standard uil Company (Ohio) and

entered the University of Florida to undertake graduate

studies leading to the degree of Doctor of Philsophy, he

is a nieiber of rhi Luambda Upsilon, Phi ;appa bhi, Tau

Beta i'i, and tihe American Chemical Society, a junior ir.eber

of tLoe .nerican Institute of Chemical ;n-ineers, an

associate :r;Oibher of i'inma Xi, and a :e.-istered Professional

n,-.ii-ier in t c .tate of Ohio.










This dissertation was prepared under the direction

of the Chairman of the candidate's Supervisory Committee
and has been approved by all members of the Committee.
It was submitted to the Graduate Council and was approved

as partial fulfillment of the requirements for the degree
of Doctor of philosophy,

Date 91 t Z /9L /


Dean_

SUs ERVISURY CO,:IT''E-.


Chairman

64J l e


/ /7

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...../

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a--~c~















ENGINEERING
SCIENCES












































UNIVERSITY OF FLORIDA


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